Tertiary hexyl alcohol-formaldehyde condensation product and method for preparing the same



'ratio as low as two to one.

Patented Nov. 9, 1943 TERTIARY HEXYL ALCOHOL-FORMALDE- HYDE CONDENSATIONPRODUCT AND METHOD FOR PREPARING THE SAME Mortimer T. Harvey,"EastOrange, N. 1., assignor to Hand Research Corporation, a corporation I ofNew Jersey No Drawing. Original application mm- 10,

1942, Serial No. 461,597.

Divided and this 8! piication October 10, 1942, Serial No. 461,599

7 Claims. This invention relates to methods of making condensationproducts of tertiary aliphatic alcohols and formaldehyde and to theproducts of such methods. The present application is a division of myapplication Serial No. 461,597 filed October 10, 1942,

Heretofore, it has been proposed to react tertiary aliphatic alcoholswith formaldehyde under anhydrous conditions and in the presence of amineral acid. In Example 6 of the United States patent to Ellis2,143,870, the patentee describes the treatment underanhydrousconditions of tertiary butyl alcohol with trioxymethylene inthepresence of hydrochloric acid, and claims to have obtaineddi-tertiary;-but$*l formal.

I have discovered that novel products may be obtained by employing newmethods pf treating a tertiary alcohol with formaldehyde. According tomy novel methods, tertiary hexyl alcohol may be treated with an aqueoussolution of formfor. one hour.

how they are produced, for which the following are given as illustrativeexamples. Example 1.One mole tertiary hexyl alcohol and one mole offormaldehydev at one hundredv pounds pressure. The tertiary hexylalcohol used in this and the following examples was diethyl methylcarbinol with a boiling point of 123 C. Tertiary hexyl alcohol ..grams'About 306 Formaldel'wde solution (It'l /2% y weight) grams About 240Sulphuric acid (cone) cc About 3.0

were heated together in an autoclave to 100:

pounds per square inch pressure and held there room temperature. No odorof formaldehyde remained. The mixture separated into two layers aldehydein the presence of a mineral acid. By

employing these methods, I have found that one mole of tertiary hexylalcohol will completely re-- act with more than one mole and with ashigh as about four to seven moles of the formaldehyde in aqueoussolution. In the course of my experimentations, I have discovered thatwhen a mixture of tertiary hexyl alcohol and aqueous solution offormaldehyde is heated in the presence of a catalyst such as a mineralacid, the formaldehyde and-the alcohol react to produce a product whichcontinues to reactwith the formaldehyde notwithstanding the presence ofunreacted alcohol. This reaction continues until more than one mole ofthe formaldehyde has i completely reacted with one mole of tertiaryhexyl alcohol, where the mole ratio of formalde-" hyde to the alcohol isgreater than oneand even in those cases. where equimolecular proportionsof the alcohol and formaldehyde are used, and also in those cases wherethe alcohol and formaldehyde in aqueous solution were present in the.According to this invention, it has been found preferable to employ oneto eight moles of formaldehyde in aqueous solution to one part oftertiary hexyl aleohol. when the eight or more moles of formaldehyde inaqueoussolution was employed with one mole of tertiary hexyl alcohol, itwas found that it ww' in excess of that which would react with thealcohol and therefore a proportion thereof products thereof can bedisclosed best by showing and was neutralized by the addition of dilutesodium hydroxide. 329 grams (specific gravity of 0.874 at 25 C.) wasdistilled to vapor temperature of 135 C, The residue, amounting to 166grams (specific gravity 0.955) .was soluble in alcohol, benzene andgasoline but insoluble in water. A portion ofthe residue oil distilledat atmospheric pressure gave the following results:

Pereentdistilled 10 20 30 40 60 so C 143 167 213 233 244 Example 2. Onemole of tertiary hexyl alcohol and three moles of'formaldehyde at onehunderd pounds pressure.

Tertiary hexyl alcohol '.grams About 306 Formaldehyde solution (37%)-do; About'720 Sulphuric acid (cone) -cc About 1.5

were heated in an autoclave to one hundred pounds per square'inchpressure and held there for one hour. The mixture was then cooled toroom temperature. No odor of.forma1dehyde'remained. The mixtureseparated into two layers. It was then neutralized by additionohiilutesodium hydroxide and the top oil layer-which separated amountedto 405 grams (specific jgravity 0992). This oil layer. was thendistilled'to va- P I temperature of 135 C.- The residue amounting to 325grams (specific gravity of 1.030) was soluble in alcohol, benzene andgasoline but insoluble in water. The distillate. was'also waterinsoluble. The residue 011, at atmospheric'pressure gave the followingresults:

gi -cementum so 00 10 so 00 101-20 so 40 ivsiaiziommmaoaasoauo Example3.-One mole of hexyl alco- The mixture was then cooled to The oil layer,amounting to aaa aoao f ularproportionsarecondensedwiththealcohol in themethod or this invention.

hol and eight lormaldehyde at one hundred pounds pressure. p g

Tertiary hexyl alcohol grams About 163 m f m' of pmdum balmFormaldehydesolution (ammmein About m 135 by the W W- ccuAbout 0.75 5invention are all close to, or greater than one,

v whereas the i'ormals of alcohols having from were heated in anautoclave to one'hundred pounds per square inch pressure and held therefor one hour:

tour to six carbon atoms which have been de- K scribed in theliterature. all have specific gravi- The mixture was then cooledto tiesbelow 0.85. Thus, according to Arnhold in 1'00!!! temperafllre d a 8M 1'0f ioi'm l- In "Annalen der Chemie" vol. 240, page 208 (1887). dehyderemained. Thebottom oill ayerwas neuthe formal or isobutyl alcohol has adensity or tralized by the addition of dilute sodium hydrox- 0.824 andisoamyl alcohol a density ct 0.036.

ids and sep at d. yie ins 2 ma p ifi The products boiling above 136' 6.obtained gravity 1.072). This oil layer was then distilled inaccordancewith the methods of the present, t atmmherlc p essure to avapor-temperature invention have been round to be solvents for such 01'135' C. The residue was a brown viscous oil materials as cellulosenitrate, ethyl cellulose. cel- -weighing 181 grams (specific gravity1.000 at 25 lulose acetate, polyvinyl esters and some gradesoixpolyvinyl alcohol. 4 e I claim:

0.). The distillate to135' Q. was water soluble.

The residue oil, distilled at atmospheric pressuregave the lollowingresults:

20 1. The method for producing an organic conmmmwwm m mmd mifliue 2 ww.m w m MW M MWW mmm w w mm mm m 2 mm ew smmm ism. m mmw mmmmwmwMW WMM WEM MKW MM m d w 1 m h m i m m s... New am. m m s m m w a mm th Rrmmmmmmwmmmmmm a m m mm mwm mm WWW m ommasmmm mw mmm w some some.. n ma.m m mmmm mmmmmimwm mammmmmwmi mmm mmm m .n w u w w n am i a i a e fie MmWW WMWWWWMMW mmmmwmm m fim m mam mum m m mm w m mm a. mm e mmm m: mm WWWews a L n a; e mm mmmmma m N am m w en n... wa ms W a Wmmw mmwmm m mmmememm m mw mm m mm mm mmmmimmmmm mmmmmmmmew mm wmmm mm m. as

